108504 20211122153226.0 doi 10.1039/d0dt03326j sideral 122418 ART-2020-122418 eng Guzmán, J. Universidad de Zaragoza (orcid)0000-0001-9340-5952 2-Pyridone-stabilized iridium silylene/silyl complexes: Structure and QTAIM analysis 2020 Iridium(III) complexes of the general formula [Ir(X)(κ2-NSiiPr2)2] (NSiiPr2 = (4-methyl-pyridine-2-yloxy)diisopropylsilyl; X = Cl, 3; CF3SO3, 5; CF3CO2, 6) have been prepared and fully characterized, including X-ray diffraction studies and theoretical calculations. The presence of isopropyl substituents at the silicon atom favours the monomeric structure found in complexes 3 and 5. The short Ir–Si bond distances (2.25–2.28 Å) indicate some degree of base-stabilized silylene character of the Ir–Si bond in 3, 5 and 6 assisted by the 2-pyridone moiety. However, the shortening of these Ir–Si bonds might be a consequence of the constrained 2-pyridone geometry, and consequently the silyl character of these bonds can not be excluded. A DFT theoretical study on the nature of the Ir–Si bonds has been performed for complex 3 as well as for four other iridium complexes finding representative examples of different bonding situations between Ir and Si atoms: silylene, base-assisted silylene (both with an anionic base and with a neutral base), and silyl bonds, using the topological properties of the electron charge density. The results of these studies show that the Ir–Si bonds in Ir–NSiiPr2 complexes can be considered as an intermediate between the base-stabilized silylene and silyl cases, and therefore they have been proposed as 2-pyridone-stabilized iridium silylene/silyl bonds. Access copy available to the general public Unrestricted info:eu-repo/grantAgreement/ES/DGA-FSE/E42-20R info:eu-repo/grantAgreement/ES/MINECO-FEDER/PGC2018-099383-B-I00 info:eu-repo/semantics/openAccess All rights reserved http://www.europeana.eu/rights/rr-f/ 4.39 2020 CHEMISTRY, INORGANIC & NUCLEAR 8 / 45 = 0.178 2020 Q1 T1 0.98 2020 Inorganic Chemistry 2020 Q1 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion Bernal, A.M. García-Orduña, P. Universidad de Zaragoza (orcid)0000-0002-7063-1292 Lahoz, F.J. Universidad de Zaragoza (orcid)0000-0001-8054-2237 Polo, V. Universidad de Zaragoza (orcid)0000-0001-5823-7965 Fernández-Alvarez, F.J. Universidad de Zaragoza (orcid)0000-0002-0497-1969 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 2012 755 Universidad de Zaragoza Dpto. Química Física Área Química Física 49, 48 (2020), 17665-17673 Dalton Trans. Dalton Transactions 1477-9226 305060 http://zaguan.unizar.es/record/108504/files/texto_completo.pdf Postprint 2458547 http://zaguan.unizar.es/record/108504/files/texto_completo.jpg?subformat=icon icon Postprint oai:zaguan.unizar.es:108504 articulos driver 2021-11-22-14:00:30 ARTICLE